EP0517987A1 - Verfahren zur Herstellung wässriger Dispersionen von magnetischen Polymerpartikeln mit verengerter Grössenverteilung - Google Patents

Verfahren zur Herstellung wässriger Dispersionen von magnetischen Polymerpartikeln mit verengerter Grössenverteilung Download PDF

Info

Publication number
EP0517987A1
EP0517987A1 EP91420195A EP91420195A EP0517987A1 EP 0517987 A1 EP0517987 A1 EP 0517987A1 EP 91420195 A EP91420195 A EP 91420195A EP 91420195 A EP91420195 A EP 91420195A EP 0517987 A1 EP0517987 A1 EP 0517987A1
Authority
EP
European Patent Office
Prior art keywords
particles
dispersion
distribution
surfactant
solid phase
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP91420195A
Other languages
English (en)
French (fr)
Other versions
EP0517987B1 (de
Inventor
Jérôme Bibette
Gilbert Schorsch
Dominique Charmot
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Prolabo SA
Original Assignee
Rhone Poulenc Chimie SA
Prolabo SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhone Poulenc Chimie SA, Prolabo SA filed Critical Rhone Poulenc Chimie SA
Publication of EP0517987A1 publication Critical patent/EP0517987A1/de
Application granted granted Critical
Publication of EP0517987B1 publication Critical patent/EP0517987B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/44—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S530/00—Chemistry: natural resins or derivatives; peptides or proteins; lignins or reaction products thereof
    • Y10S530/81—Carrier - bound or immobilized peptides or proteins and the preparation thereof, e.g. biological cell or cell fragment as carrier
    • Y10S530/812—Peptides or proteins is immobilized on, or in, an organic carrier
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S530/00—Chemistry: natural resins or derivatives; peptides or proteins; lignins or reaction products thereof
    • Y10S530/81—Carrier - bound or immobilized peptides or proteins and the preparation thereof, e.g. biological cell or cell fragment as carrier
    • Y10S530/812—Peptides or proteins is immobilized on, or in, an organic carrier
    • Y10S530/815—Carrier is a synthetic polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y10T428/2995—Silane, siloxane or silicone coating

Definitions

  • the subject of the present invention is a process for the preparation of aqueous dispersions of particles of magnetizable polymer of tight distribution from aqueous dispersions of spread distribution of said particles.
  • Polymer microspheres are used in making diagnostic tests of the Radio Immuno Assay or Immnuno Enzymatic type; the separation and washing steps are simplified when these microspheres are magnetizable.
  • the efficiency of these microspheres is all the more important as the particle size thereof is more tight; indeed, a good particle size tightening makes it possible to obtain a clear sedimentation front and a supernatant phase free of fine particles, while limiting the phenomenon of sedimentation due to large particles.
  • the monodispersity in size allows access to the exact adsorption surface of the microspheres and therefore to the optimal binding capacity of these vis-à-vis antigens or antibodies.
  • magneto-thickening fluids based on suspensions of magnetizable polymer particles the best performance is achieved when the magnetizable particles have a tight particle size.
  • European Patent No. 38730 describes a process for preparing latexes of magnetizable polymers which consists in dispersing the magnetic charge in an organic phase containing an organosoluble initiator and / or the monomer (s), in mixing the dispersion with a aqueous solution formed of water and emulsifier, to homogenize the mixture to obtain droplets of organic phase of size between 0.03 and 5 micrometers and finally polymerization after addition of monomer (s) if necessary.
  • the size of the final particles corresponds to that of the droplets.
  • Homogenization is carried out in a homogenizer with high shearing power (colloid mill for example); the droplets (therefore the polymer particles) have a distribution which is a function of the rate of emulsifier and of the organic phase / aqueous phase ratio.
  • the particle size distribution of the polymer particles obtained according to this process is generally spread out.
  • the object of the invention is therefore to obtain tight distributions of particles (standard deviation less than or equal to 30%, preferably of the order of 15 to 25%, or even of the order of 3 to 5% in increasing the number of splits).
  • aqueous dispersions of initial spread distribution can be prepared by any known method; we can cite in particular the modes procedures described in European patent n ° 38730, French patent application n ° 89.04231 dated 31.3.1989, French patent applications published under the numbers 2.618.084 and 2.624.873.
  • the particles of the starting aqueous dispersions can have a particle size of the order of 0.01 to 20 ⁇ m and preferably of the order of 0.1 to 3 ⁇ m.
  • organopolysiloxanes as well as polymers derived from monomer (s) immiscible with water (that is to say solubility in water less than 5 % in weight).
  • the monomer composition from which said polymer is derived may also contain up to 10% of its weight (preferably up to 4% of its weight) of at least one monomer carrying ionogenic or reactive groups such as: -SO3H, -OSO3H, - NOT + R3, -COOH, -OH, -NH2, -NR2, -CONH2, -SH, -COOR, -PO (OR) 2, R representing a C1 - C4, preferably C1 - C2, alkyl radical.
  • ionogenic or reactive groups such as: -SO3H, -OSO3H, - NOT + R3, -COOH, -OH, -NH2, -NR2, -CONH2, -SH, -COOR, -PO (OR) 2, R representing a C1 - C4, preferably C1 - C2, alkyl radical.
  • the level of surfactant in the aqueous dispersions of initial spread distribution is between 0.1 and 2 times the CMC (critical micellar concentration: concentration of surfactant necessary for the appearance of the first aggregates of surfactant -active called micelles).
  • These surfactants which ensure the stability of the dispersion, can be anionic, cationic, amphoteric or non-ionic.
  • anionic surfactants that may be mentioned are alkali metal alkylbenzenesulfonates, alkali metal alkylsulfates such as sodium dodecylsulfate, alkali metal alkylethersulfates, alkali metal alkylarylethersulfates and alkali metal dioctylsulfosuccinates.
  • cationic surfactants that may be mentioned are dialkyl (C10-C30) benzyldimethylammonium halides and polyethoxylated quaternary ammonium salts.
  • amphoteric surfactants mention may be made of N-alkyl (C10-C22) betaines, N-alkyl (C10-C22) amidobetaines, alkyl (C10-C22) imidazolines and asparagine derivatives.
  • nonionic surfactants that may be mentioned are polyethoxylated fatty acids, sorbitan esters, polyethoxylated sorbitan esters, polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyethoxylated or polyglycerolated fatty amides, polyglycerolated alcohols and alphadiols.
  • the amount of surfactant to be introduced in step b) is that necessary to obtain two phases, a liquid phase where the particles are free and a solid phase where the particles are combined.
  • step a) an amount of surfactant such that the concentration of surfactant reaches 2.5 to 20 times the CMC and preferably on the order of 2.5 to 10 times the CMC.
  • the surfactant used can be the same or those as that or those of the starting dispersion or any surfactant compatible with that or those of departure. Examples of surfactants have been given above.
  • the two phases are then separated by any means, pumping, suction, etc., the settling being possibly accelerated by a magnetic field.
  • Operations a), b) and c) are optionally repeated on the separated solid phase as many times as necessary to obtain the desired tight distribution dispersion.
  • This solid phase is optionally homogenized and diluted with water to obtain a single-phase dispersion where the particles are well separated.
  • the solid phase or phases thus separated by the process of the invention have an increasingly tight distribution.
  • the size of the particles of the solid phase is measured for example by optical microscopy or using suitable granulometers.
  • the more or less tight character is evaluated by the rate of polydispersity.
  • liquid phase recovered in c) can be considered as the starting dispersion of step a) but devoid of the population of particles recovered in the solid phase. Consequently, it is possible on this liquid phase to apply steps b) and c) of the process of the invention at least once.
  • the solid phases generated by increasing concentrations of surfactant will consist of increasingly small particles. This being a consequence of the action of the surfactant and constitutes the basis of the method according to the invention.
  • the result is obtained by repeating from 1 to 8 times (more generally from 2 to 5 times) steps a), b) and c) on the fluid phase and / or the solid phase.
  • step c) the recovered fluid phase is reprocessed as in b) this time bringing the concentration CS of SLS to 0.04 mole / liter, then step c) is linked as before.
  • the operating cycle b), c) is repeated again 2 times on the fluid phase to arrive at a concentration C4 in SLS of 0.08 mole / liter.
  • the solid phase recovered at the end of this last operation is then redispersed in distilled water; the size distribution of the magnetic particles is analyzed using a Brookhaven ® DCP 1000 centrifugal photosedimentometer marketed by Brookhaven Inst. Corp.
  • the size distribution curve is shown in fig 1.
  • Curve a) represents the cumulative distribution curve by weight, curve b) that of weight distribution.
  • the aqueous dispersion of magnetic microspheres bears the reference ESTAPOR® M1-070 / 60.
  • the content of magnetic oxide is around 60% by weight.
  • the particle size distribution is polydisperse with diameters typically between 0.05 micrometer and 3 micrometers and about 70% by weight of the microspheres having a diameter between 0.3 micrometer and 1 micrometer; the average size by weight is of the order of 0.7 micrometer.
  • the solid phase recovered is redispersed to a dry extract of the order of 5% by weight.
  • SLS is added to a concentration of 0.05 mole / liter.
  • the suspension is left to stand for 15 hours, the decanted solid phase is recovered and redispersed in distilled water; the size distribution of the magnetic particles is analyzed using a Brookhaven ® DCP 1000 centrifugal photosedimentometer.
  • the degree of polydispersity is estimated at 35% (compared to 50% for the initial dispersion).
  • Example 2 To the dispersion recovered at the end of the treatment of Example 2, SLS is added up to a concentration of 0.06 mol / liter. We then proceed to operation c) of Example 1; the solid phase is recovered, treated according to operations a) and b) of Example 1 at an SLS concentration of 0.06 mol / liter and then followed by operation c) as above to recover a solid fraction.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Colloid Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP91420195A 1990-02-14 1991-06-14 Verfahren zur Herstellung wässriger Dispersionen von magnetischen Polymerpartikeln mit verengerter Grössenverteilung Expired - Lifetime EP0517987B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR9001725A FR2658200B1 (fr) 1990-02-14 1990-02-14 Procede de preparation de dispersions aqueuses de particules de polymere magnetisable de distribution resserree.

Publications (2)

Publication Number Publication Date
EP0517987A1 true EP0517987A1 (de) 1992-12-16
EP0517987B1 EP0517987B1 (de) 1995-09-13

Family

ID=9393688

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91420195A Expired - Lifetime EP0517987B1 (de) 1990-02-14 1991-06-14 Verfahren zur Herstellung wässriger Dispersionen von magnetischen Polymerpartikeln mit verengerter Grössenverteilung

Country Status (6)

Country Link
US (1) US5242964A (de)
EP (1) EP0517987B1 (de)
JP (1) JPH0776267B2 (de)
DE (1) DE69113033T2 (de)
ES (1) ES2078485T3 (de)
FR (1) FR2658200B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019103903A1 (en) 2017-11-27 2019-05-31 Cargill, Incorporated Double emulsions

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4037518C2 (de) * 1989-11-27 1998-12-17 Toyo Boseki Polymerteilchen, Verfahren zu deren Herstellung und Verwendung derselben
JP3367987B2 (ja) * 1993-02-15 2003-01-20 コニカ株式会社 顔料含有重合体粒子およびその製造方法、電子写真用トナー並びに免疫学的診断試薬用担体
FR2735778B1 (fr) * 1995-06-22 1997-08-22 Prolabo Sa Nouveau latex de microspheres magnetisables monodisperses calibrees, procede de preparation et utilisation dudit latex en chimie ou en biologie
CA2260991C (en) * 1997-11-18 2009-03-24 Bio-Rad Laboratories, Inc. Multiplex flow immunoassays with magnetic particles as solid phase
FR2798601B1 (fr) * 1999-09-20 2001-12-21 Centre Nat Rech Scient Emulsion double polydisperse, emulsion double monodisperse correspondante et procede de preparation de l'emulsion monodisperse
JP5543021B2 (ja) * 2010-06-13 2014-07-09 オーシャンズ キング ライティング サイエンスアンドテクノロジー カンパニー リミテッド コアシェル型磁性合金ナノ粒子の調製方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1416004A (en) * 1973-01-31 1975-12-03 Commw Scient Ind Research Preparation of polymer composites
EP0038730A1 (de) * 1980-04-18 1981-10-28 Rhone-Poulenc Specialites Chimiques Latex magnetischer Polymere und Verfahren zur Herstellung
DD155073A1 (de) * 1980-12-05 1982-05-12 Klaus Tauer Verfahren zur fraktionierung von latices
EP0291389A1 (de) * 1987-05-11 1988-11-17 Rhone-Poulenc Chimie Polymerpartikel mit in ihren Oberflächen eingepflanzten amphiphilen Molekülen, die ionogene oder reaktive Gruppen enthalten, Verfahren zur Herstellung derselben und Anwendungen in der Biologie
EP0299846A1 (de) * 1987-07-15 1989-01-18 Rhone-Poulenc Chimie Magnetisierbare Polysiloxanmikrokugel und Verfahren zur Herstellung und die Anwendung derselben

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR38730E (fr) * 1930-06-26 1931-07-04 Le Matin Perfectionnements aux creusets des machines à fondre les caractères
GB1582956A (en) * 1976-07-30 1981-01-21 Ici Ltd Composite magnetic particles
US4554088A (en) * 1983-05-12 1985-11-19 Advanced Magnetics Inc. Magnetic particles for use in separations

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1416004A (en) * 1973-01-31 1975-12-03 Commw Scient Ind Research Preparation of polymer composites
EP0038730A1 (de) * 1980-04-18 1981-10-28 Rhone-Poulenc Specialites Chimiques Latex magnetischer Polymere und Verfahren zur Herstellung
DD155073A1 (de) * 1980-12-05 1982-05-12 Klaus Tauer Verfahren zur fraktionierung von latices
EP0291389A1 (de) * 1987-05-11 1988-11-17 Rhone-Poulenc Chimie Polymerpartikel mit in ihren Oberflächen eingepflanzten amphiphilen Molekülen, die ionogene oder reaktive Gruppen enthalten, Verfahren zur Herstellung derselben und Anwendungen in der Biologie
EP0299846A1 (de) * 1987-07-15 1989-01-18 Rhone-Poulenc Chimie Magnetisierbare Polysiloxanmikrokugel und Verfahren zur Herstellung und die Anwendung derselben

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019103903A1 (en) 2017-11-27 2019-05-31 Cargill, Incorporated Double emulsions

Also Published As

Publication number Publication date
DE69113033D1 (de) 1995-10-19
JPH0776267B2 (ja) 1995-08-16
JPH04359925A (ja) 1992-12-14
US5242964A (en) 1993-09-07
ES2078485T3 (es) 1995-12-16
EP0517987B1 (de) 1995-09-13
FR2658200B1 (fr) 1992-07-24
DE69113033T2 (de) 1996-05-15
FR2658200A1 (fr) 1991-08-16

Similar Documents

Publication Publication Date Title
EP0038730B1 (de) Latex magnetischer Polymere und Verfahren zur Herstellung
EP0390634B1 (de) Magnetisierbare Mikrokugeln aus vernetztem, hydrophobem Polymer, Verfahren zu ihrer Herstellung und ihre Verwendung in der Biologie
EP1397429B1 (de) Verbundteilchen, konjugate, verfahren zur herstellung und verwendungen
Cullis et al. Effects of fusogenic agent on membrane structure of erythrocyte ghosts and the mechanism of membrane fusion
US5851538A (en) Retinoid formulations in porous microspheres for reduced irritation and enhanced stability
CN110846028B (zh) 高分子包覆钙钛矿量子点及其制备方法和包括其的半导体发光材料
Buitenhuis et al. Phase separation of mixtures of colloidal boehmite rods and flexible polymer
EP0517987B1 (de) Verfahren zur Herstellung wässriger Dispersionen von magnetischen Polymerpartikeln mit verengerter Grössenverteilung
Gallardo et al. Study of the mechanisms of formation of nanoparticles and nanocapsules of polyisobutyl-2-cyanoacrylate
EP1053277B1 (de) Ein aktives material enthaltende verbundpartikel
FR2689418A1 (fr) Procédé de préparation de micro-capsules ou de liposomes de tailles contrôlées par application d'un cisaillement constant sur une phase lamellaire.
EP0777691B1 (de) Polymerisationsverfahren zur herstellung von kalibriertem monodispersem latex
Poulain et al. Nanoparticles from vesicle polymerization: Characterization and kinetic study
FR2691969A1 (fr) Nanoparticules de polymères fonctionnalisées, leur procédé de préparation et leur utilisation.
JPH0273872A (ja) メタリック顔料用整粒金属粉末及び整粒金属粉末の製造方法
Mayer et al. Oligonucleotide-protamine-albumin nanoparticles: Protamine sulfate causes drastic size reduction
EP0436449B1 (de) Magnetisierbare Polysilsesquioxanmikrokugeln, Verfahren zu ihrer Herstellung und ihre Verwendung in der Biologie
CN1318459C (zh) 纳米二氧化硅－丙烯酸酯高分子微球材料的制备方法
JP2002507242A (ja) ポリマー性材料及びそれらの用途
Ahire et al. An overview on methods of preparation and characterization of nanoemulsion
US20110177306A1 (en) Novel Core-Shell Structure
US3970577A (en) Water-dispersible aluminium pastes
Nouri et al. How an organogelator can gelate water: gelation transfer from oil to water induced by a nanoemulsion
IE911906A1 (en) Process for the preparation of aqueous dispersions of¹magnetizable polymer particles with a narrow distribution
CA2453005A1 (fr) Procede hydrometallurgique de separation des poussieres d`acieries utilisant un four a arc et pigments obtenus par le procede

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE DK ES FR GB IT NL SE

17P Request for examination filed

Effective date: 19930204

17Q First examination report despatched

Effective date: 19930624

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SOCIETE PROLABO

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SOCIETE PROLABO

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE DK ES FR GB IT NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19950913

Ref country code: DK

Effective date: 19950913

REF Corresponds to:

Ref document number: 69113033

Country of ref document: DE

Date of ref document: 19951019

ITF It: translation for a ep patent filed

Owner name: CON LOR S.R.L.

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19951213

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2078485

Country of ref document: ES

Kind code of ref document: T3

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19951127

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19960630

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
BERE Be: lapsed

Owner name: SOC. PROLABO

Effective date: 19960630

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19970602

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19970606

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19970623

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980614

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 19980615

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19980614

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990401

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20000201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050614

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20100709

Year of fee payment: 20